EP0011071A1 - Manganese dioxide electrode for electrochemical generators and methods for producing the same - Google Patents

Manganese dioxide electrode for electrochemical generators and methods for producing the same Download PDF

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Publication number
EP0011071A1
EP0011071A1 EP78400181A EP78400181A EP0011071A1 EP 0011071 A1 EP0011071 A1 EP 0011071A1 EP 78400181 A EP78400181 A EP 78400181A EP 78400181 A EP78400181 A EP 78400181A EP 0011071 A1 EP0011071 A1 EP 0011071A1
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EP
European Patent Office
Prior art keywords
manganese dioxide
felt
mass
weaving
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP78400181A
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German (de)
French (fr)
Inventor
Société de Recherche et d'Applications Electrochimiques SORAPEC
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SORAPEC SA
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Societe de Recherches et dApplications Electronchimiques SORAPEC SA
SORAPEC SA
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Priority to EP78400181A priority Critical patent/EP0011071A1/en
Publication of EP0011071A1 publication Critical patent/EP0011071A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal

Definitions

  • the invention which is the subject of this patent relates to electrochemical cells. It applies more particularly to generators whose positive electrode is depolarized by manganese dioxide. In such generators, the positive mass, by virtue of its structure, is the source of a certain number of drawbacks which the object of the present invention is to overcome.
  • the conventional architecture of the positive electrode comprises, around a positive current collector constituted by a graphite rod, a mass of carbon black and manganese dioxide.
  • carbon black is precisely used for its properties of electronic conductor.
  • each of its particles must be in intimate contact with particles of carbon black, ensuring conduction.
  • the volume allocated to the depolarizer cannot normally exceed approximately 60% of that of the positive mass. To achieve the desired capacities for the type of generator in question, it is therefore necessary to devote a large volume to the mass, which is not without drawback and practically prohibits the use of this process for the production of "batteries miniaturized ".
  • the yield obtained is poor because all the particles of manganese dioxide are not called to work in the same way: in fact, the resistance that meets the current on the route which separates each particle from the collector increases with distance due to the imperfect conductivity of carbon black. The parts ⁇ The cells closest to the collector will therefore be exhausted and the battery "discharged" before the most distant particles can be used.
  • the present invention overcomes all of these drawbacks by replacing carbon black with a network of fibers of the weaving or conductive felt type, serving as a support for a deposit of manganese dioxide and placed in contact with the current collector.
  • a network of fibers of the weaving or conductive felt type serving as a support for a deposit of manganese dioxide and placed in contact with the current collector.
  • the depolarizer produced by electrolysis can be formed at the anode of the electrolytic cell directly on the carbon felt which will be subsequently used in the cell.
  • the electrolyte used may in particular be a molar solution of manganese sulfate and sulfuric acid.
  • the electrolysis is carried out at a temperature of 90 ° C., under a current density of 10 mA per square centimeter of apparent surface of felt. It may be recalled here that there are different varieties of manganese dioxide; among the most active as depolarizing agent for electric batteries is that obtained by electrolytic means.
  • the deposit obtained on the felt which has great homogeneity and regularity, offers considerable advantages compared to the conventional positive mass.
  • the volume left free inside the felt can represent more than 80% of the whole.
  • the essential advantage consists in the possibility of a considerable increase in capacity due to the very structure of the new mass.
  • the powdery deposit is fixed directly and very intimately on the fibers of the felt.
  • the flow of the current being done along and by each of the fibers of the felt, this structure allows obtaining a great homogeneity of the electric field, all the particles of the pulverulent deposit of manganese dioxide working in the same way and at maximum efficiency. .
  • the discharge curves obtained are of the type represented by FIG. 1, which corresponds to the operation of a "micropile" of 1 cm 2 of useful surface under I mA. They have a plateau located at 1.2 V which is not possible to obtain the conventional positive masses with manganese dioxide.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Positive electrode comprising manganese dioxide attached in the form of a deposit onto a backing made from conductive fibres of the woven fabric or felt type, such as carbon or graphite fibres. The manganese dioxide is deposited by electrolysis of a solution containing a manganese salt, by electrophoresis or by impregnating the backing with a solution containing manganese dioxide in suspension.

Description

L'invention, objet du présent brevet concerne les piles électrochimiques. Elle s'applique plus particulièrement aux générateurs dont l'électrode positive est dépolarisée par du bioxyde de manganèse. Dans de tels générateurs, la masse positive, de par sa structure, est à l'origine d'un certain nombre d'inconvénients que la présente invention a pour objectif de pallier.The invention which is the subject of this patent relates to electrochemical cells. It applies more particularly to generators whose positive electrode is depolarized by manganese dioxide. In such generators, the positive mass, by virtue of its structure, is the source of a certain number of drawbacks which the object of the present invention is to overcome.

Dans les piles actuelles à cathode au bioxyde de manganèse, l'architecture classique de l'électrode positive comprend, autour d'un collecteur de courant positif constitué par un barreau de graphite, une masse de noir de carbone et de bioxyde de manganèse. Dans cette masse où le bioxyde de manganèse tient le rôle du dépolarisant mais présente une très mauvaise conductibilité électronique, le noir de carbone est précisément utilisé pour ses propriétés de conducteur électronique. Pour une efficacité maximale du dépolarisant, chacune de ses particules doit être en contact intime avec des particules de noir de carbone, assurant la conduction. Le volume dévolu au dépolarisant ne peut ainsi normalement dépasser environ 60 % de celui de la masse positive. Pour atteindre les capacités souhaitées pour le type de générateur en question, il est par conséquent nécessaire de consacrer un fort volume à la masse, ce qui n'est pas sans inconvénient et interdit pratiquement l'utilisation de ce procédé pour la réalisation de "piles miniaturisées".In current manganese dioxide cathode batteries, the conventional architecture of the positive electrode comprises, around a positive current collector constituted by a graphite rod, a mass of carbon black and manganese dioxide. In this mass where the manganese dioxide plays the role of depolarizer but has very poor electronic conductivity, carbon black is precisely used for its properties of electronic conductor. For maximum effectiveness of the depolarizer, each of its particles must be in intimate contact with particles of carbon black, ensuring conduction. The volume allocated to the depolarizer cannot normally exceed approximately 60% of that of the positive mass. To achieve the desired capacities for the type of generator in question, it is therefore necessary to devote a large volume to the mass, which is not without drawback and practically prohibits the use of this process for the production of "batteries miniaturized ".

De surcroît, le rendement obtenu est mauvais car toutes les particules de bioxyde de manganèse ne sont pas appelées à travailler de la même façon : en effet, la résistance que rencontre le courant sur l'itinéraire qui sépare chaque particule du collecteur croît avec la distance du fait de la conductibilité imparfaite du noir de carbone. Les part~ cules les plus proches du collecteur seront donc épuisées et la pile "déchargée" avant que les particules les plus éloignées aient pu être utilisées.In addition, the yield obtained is poor because all the particles of manganese dioxide are not called to work in the same way: in fact, the resistance that meets the current on the route which separates each particle from the collector increases with distance due to the imperfect conductivity of carbon black. The parts ~ The cells closest to the collector will therefore be exhausted and the battery "discharged" before the most distant particles can be used.

La présente invention permet de pallier l'ensemble de ces inconvénients grâce au remplacement du noir de carbone par un réseau de fibres du type tissage ou feutre conducteur, servant de support à un dépôt de bioxyde de manganèse et placé au contact du collecteur de courant. On s'attachera, à titre d'exemple non limitatif d'application du procédé, objet du présent brevet, à mettre en évidence les avantages de celui-ci par rapport au dispositif habituel dans le cas de l'utilisation d'un feutre de carbone, et on décrira un mode de réalisation préférentiel de la masse, n'ayant aucun caractère restrictif.The present invention overcomes all of these drawbacks by replacing carbon black with a network of fibers of the weaving or conductive felt type, serving as a support for a deposit of manganese dioxide and placed in contact with the current collector. We will endeavor, by way of nonlimiting example of application of the method which is the subject of this patent, to highlight the advantages of the latter compared to the usual device in the case of the use of a felt. carbon, and a preferred embodiment of the mass will be described, having no restrictive character.

Selon ce procédé de fabrication qui consiste en une électrodéposition du bioxyde de manganèse sur le feutre, le dépolarisant produit par électrolyse peut être formé à l'anode de la cuve électrolytique directement sur le feutre de carbone qui sera ultérieurement utilisé dans la pile. L'électrolyte utilisé pourra notamment être une solution molaire de sulfate de manganèse et d'acide sulfurique. L'électrolyse est effectuée à une température de 90°C, sous une densité de courant de 10 mA par centimètre carré de surface apparente de feutre. On peut rappeler ici qu'il existe différentes variétés de bioxyde de manganèse; parmi les plus actives en tant que dépolarisant pour piles électriques se trouve celle qui est obtenue par voie électrolytique.According to this manufacturing process which consists of electrodeposition of manganese dioxide on the felt, the depolarizer produced by electrolysis can be formed at the anode of the electrolytic cell directly on the carbon felt which will be subsequently used in the cell. The electrolyte used may in particular be a molar solution of manganese sulfate and sulfuric acid. The electrolysis is carried out at a temperature of 90 ° C., under a current density of 10 mA per square centimeter of apparent surface of felt. It may be recalled here that there are different varieties of manganese dioxide; among the most active as depolarizing agent for electric batteries is that obtained by electrolytic means.

Il est donc particulièrement intéressant d'utiliser cette variété et de la former directement, comme cela est possible, sur le feutre de carbone. On réduit ainsi notablement le nombre des opérations de préparation par rapport à la réalisation d'une masse positive classique. Il convient de signaler que d'autres procédés de fabrication peuvent être utilisés, parmi lesquels les formations de dépôt sur le feutre par électrophorèse ou imprégnation dans une solution de bioxyde de manganèse en suspension.It is therefore particularly interesting to use this variety and to train it directly, as possible, on carbon felt. This significantly reduces the number of preparation operations compared to achieving a conventional positive mass. It should be noted that other manufacturing processes can be used, among which the formation of deposits on the felt by electrophoresis or impregnation in a solution of manganese dioxide in suspension.

Le dépôt obtenu sur le feutre, qui présente une grande homogénéité et régularité, offre des avantages considérables par rapport à la masse positive classique.The deposit obtained on the felt, which has great homogeneity and regularity, offers considerable advantages compared to the conventional positive mass.

Ainsi, le volume laissé libre à l'intérieur du feutre, volume qu'il est donc possible de remplir de bioxyde de manganèse, peut représenter plus de 80 % de l'ensemble.Thus, the volume left free inside the felt, volume which it is therefore possible to fill with manganese dioxide, can represent more than 80% of the whole.

Par ailleurs, l'avantage essentiel consiste en une possibilité d'accroissement considérable de la capacité du fait de la structure même de la nouvelle masse. En effet, le dépôt pulvérulent se fixe directement et de façon très intime sur les fibres du feutre. Le cheminement du courant se faisant le long et par chacune des fibres du feutre, cette structure permet l'obtention d'une grande homogénéité du champ électrique, toutes les particules du dépôt pulvérulent de bioxyde de manganèse travaillant de la même manière et au rendement maximal.Furthermore, the essential advantage consists in the possibility of a considerable increase in capacity due to the very structure of the new mass. Indeed, the powdery deposit is fixed directly and very intimately on the fibers of the felt. The flow of the current being done along and by each of the fibers of the felt, this structure allows obtaining a great homogeneity of the electric field, all the particles of the pulverulent deposit of manganese dioxide working in the same way and at maximum efficiency. .

Le procédé, objet du présent dépôt, apporte donc par rapport à la masse positive classique de noir de carbone et bioxyde de manganèse une meilleure répartition du champ électrique dans l'ensemble de la nouvelle masse. Des gains considérables de capacités massique et volumique sont réalisés. Les caractéristiques de décharge d'un élément ainsi constitué s'avèrent beaucoup plus constantes au cours du fonctionnement dans le temps que dans le cas des piles à masse positive classique.The process which is the subject of this filing therefore provides, with respect to the conventional positive mass of carbon black and manganese dioxide, a better distribution of the electric field throughout the new mass. Considerable gains in mass and volume capacities are made. The discharge characteristics of an element thus formed prove to be much more constant during operation over time than in the case of conventional positive mass cells.

Les courbes de décharge obtenues sont du type de celle représentée par la figure l, qui correspond au fontionnement d'une "micropile" de 1 cm2 de surface utile sous I mA. Elles présentent un palier situé à I,2 V que ne permettent pas d'obtenir les masses positives classiques au bioxyde de manganèse.The discharge curves obtained are of the type represented by FIG. 1, which corresponds to the operation of a "micropile" of 1 cm 2 of useful surface under I mA. They have a plateau located at 1.2 V which is not possible to obtain the conventional positive masses with manganese dioxide.

La réalisation de gains volumiques par ce procédé permet l'adaptation de la pile à cathode au bioxyde de manganèse associée à divers types d'anode, par exemple de zinc, à la conception et à la fabrication de piles miniaturisées, de même qu'elle permet d'améliorer les performances des piles de type Leclanché.The achievement of volume gains by this process allows the adaptation of the cathode cell to manganese dioxide associated with various types of anode, for example zinc, to the design and manufacture of miniaturized cells, as well as improves the performance of Leclanché type batteries.

L'utilisation d'un feutre ou d'un tissage conducteur peut également être étendue aux accumulateurs à plomb, comme support d'un dépôt de bioxyde de plomb. Naturellement, et comme il résulte d'ailleurs largement de ce qui précède, l'invention n'est limitée ni aux exemples de réalisation ni aux modes d'obtention qui ont été décrits en exemple, mais en embrasse toutes les variantes.The use of a felt or conductive weaving can also be extended to lead accumulators, as a support for a deposit of lead dioxide. Naturally, and as it moreover largely follows from the above, the invention is not limited neither to the exemplary embodiments nor to the methods of obtaining which have been described in example, but embraces all the variants thereof.

Claims (5)

1 - Masse positive au bioxyde de manganèse, le générateur électrique, caractérisée par le fait que le bioxyde de manganèse est fixé sous forme d'un dépôt sur un réseau de fibres conductrices du type tissage ou feutre, placé au contact d'un collecteur de courant positif.1 - Positive mass with manganese dioxide, the electric generator, characterized in that the manganese dioxide is fixed in the form of a deposit on a network of conductive fibers of the weaving or felt type, placed in contact with a collector of positive current. 2 - Masse au bioxyde de manganèse selon la revendication 1 caractérisés par le fait que le réseau de fibres conductrices est un feutre de graphite ou carbone.2 - Manganese dioxide mass according to claim 1 characterized in that the network of conductive fibers is a graphite or carbon felt. 3 - Masse au bioxyde de manganèse, selon la revendication 1, caractérisée par le fait que le réseau de fibres conductrices est un tissage de graphite ou carbone.3 - Manganese dioxide mass, according to claim 1, characterized in that the network of conductive fibers is a weaving of graphite or carbon. 4 - Masse selon les revendications 1, 2 et 3 caractérisée par le fait que le dépôt de bioxyde de manganèse est effectué directement sur le feutre ou tissage placé en anode dans une cuve d'électrolyse contenant un sel de manganèse.4 - Mass according to claims 1, 2 and 3 characterized in that the deposition of manganese dioxide is carried out directly on the felt or weaving placed as anode in an electrolysis tank containing a manganese salt. 5 - Masse selon les revendications 1, 2 et 3 caractérisée par le fait que le dépôt de bioxyde de manganèse est effectué par électrophorèse, ou par imprégnation du feutre ou tissage dans une solution contenant du bioxyde de manganèse en suspension.5 - Mass according to claims 1, 2 and 3 characterized in that the deposition of manganese dioxide is carried out by electrophoresis, or by impregnation of the felt or weaving in a solution containing manganese dioxide in suspension.
EP78400181A 1978-11-15 1978-11-15 Manganese dioxide electrode for electrochemical generators and methods for producing the same Withdrawn EP0011071A1 (en)

Priority Applications (1)

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EP78400181A EP0011071A1 (en) 1978-11-15 1978-11-15 Manganese dioxide electrode for electrochemical generators and methods for producing the same

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EP78400181A EP0011071A1 (en) 1978-11-15 1978-11-15 Manganese dioxide electrode for electrochemical generators and methods for producing the same

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085743A (en) * 1990-05-02 1992-02-04 Physical Sciences, Inc. Electrode for current-limited cell, cell including the electrode method for using the cell and a method of making the electrode

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR465011A (en) * 1913-11-18 1914-04-06 Robert Paul Barbier New electrode system applicable to primary and secondary battery cells as well as to electrolysis and manufacturing processes
FR1114316A (en) * 1953-06-14 1956-04-11 Caroline Elisabeth Stiftung Dry battery
FR1521772A (en) * 1966-05-02 1968-04-19 Gen Electric Method of forming faure type electrodes by electrophoresis
US3481790A (en) * 1967-08-29 1969-12-02 Esb Inc Seawater reserve battery having magnesium anode and lead dioxide-graphite fabric cathode
US3485677A (en) * 1967-03-31 1969-12-23 Patent Holding Corp Dry cell battery
FR2119372A5 (en) * 1971-12-01 1972-08-04 Brenet Jean Oxide prepn - by decompsn of nitrate(s) directly onto a porous substrate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR465011A (en) * 1913-11-18 1914-04-06 Robert Paul Barbier New electrode system applicable to primary and secondary battery cells as well as to electrolysis and manufacturing processes
FR1114316A (en) * 1953-06-14 1956-04-11 Caroline Elisabeth Stiftung Dry battery
FR1521772A (en) * 1966-05-02 1968-04-19 Gen Electric Method of forming faure type electrodes by electrophoresis
US3485677A (en) * 1967-03-31 1969-12-23 Patent Holding Corp Dry cell battery
US3481790A (en) * 1967-08-29 1969-12-02 Esb Inc Seawater reserve battery having magnesium anode and lead dioxide-graphite fabric cathode
FR2119372A5 (en) * 1971-12-01 1972-08-04 Brenet Jean Oxide prepn - by decompsn of nitrate(s) directly onto a porous substrate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085743A (en) * 1990-05-02 1992-02-04 Physical Sciences, Inc. Electrode for current-limited cell, cell including the electrode method for using the cell and a method of making the electrode

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